JP5743132B2 - Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same - Google Patents

Description

  The present invention relates to a liquid crystal composition containing a polymerizable compound, and further to a liquid crystal display device using the liquid crystal composition.

  A PSA (Polymer Sustained Alignment) type liquid crystal display device has a structure in which a polymer structure is formed in a cell in order to control the pretilt angle of liquid crystal molecules, and further improvements in characteristics due to high-speed response and high contrast. Is underway.

  A PSA-type liquid crystal display device is manufactured by injecting a polymerizable composition comprising a liquid crystalline compound and a polymerizable compound between substrates and applying a voltage to polymerize the polymerizable compound in a state in which the liquid crystal molecules are aligned to produce liquid crystal molecules. This is done by fixing the orientation. In this case, the remaining amount of the polymerizable compound needs to be minimized because display persistence occurs in the manufactured display element due to the incomplete polymerization and the remaining polymerizable compound. However, if a large amount of a polymerization initiator is added to allow the polymerization to proceed completely, the residual polymerization initiator will reduce the voltage holding ratio of the display element, adversely affect the display quality, and suppress the decrease in voltage holding ratio. When the amount of the polymerization initiator used for polymerization is reduced, the polymerization does not proceed completely, so that the polymerizable compound remains, and the occurrence of image sticking by the remaining polymerizable compound is inevitable. In order to completely cure the polymerizable compound with a small addition amount of polymerization initiator and suppress the residual of the polymerizable compound, it is necessary to apply a large amount of energy by irradiating with strong ultraviolet rays for a long time in the polymerization. This leads to an increase in the size of the apparatus and a decrease in manufacturing efficiency. Therefore, in a liquid crystal composition containing a conventional polymerizable compound, it is difficult to simultaneously reduce the residual amounts of both the uncured polymerizable compound and the polymerization initiator, and polymerization can be performed without using a polymerization initiator. There has been a demand for a liquid crystal composition containing a polymerizable compound that can be completed.

  On the other hand, the occurrence of image sticking is known to be caused by the pretilt angle of liquid crystal molecules in a liquid crystal composition containing a polymerizable compound. That is, if the polymer, which is a cured product of the polymerizable compound, is flexible, the structure of the polymer will change if the same pattern is displayed for a long time when the display element is configured, and as a result, the pretilt angle will change. End up. Since the change in the pretilt angle causes burn-in, a polymerizable compound that forms a polymer having a rigid structure in which the polymer structure does not change is required.

  Conventionally, in order to prevent image sticking by improving the rigidity of a polymer, a display element is configured using a polymerizable compound having a ring structure and a structure such as a 1,4-phenylene group having only a polymerizable functional group. (See Patent Document 1) and the construction of a display element using a polymerizable compound having a biaryl structure (see Patent Document 2) have been studied. However, since these polymerizable compounds have low compatibility with the liquid crystal compound, precipitation of the polymerizable compound occurs when the liquid crystal composition is prepared, so that application as a practical liquid crystal composition is difficult. there were.

  Also, in order to prevent seizure by improving the rigidity of the polymer, a mixture of a bifunctional polymerizable compound and a trifunctional or higher functional polymerizable compound such as dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate It has been proposed to form a display element using a liquid crystal composition (see Patent Document 3). However, since dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate do not have a ring structure in the molecule, their affinity with liquid crystal compounds is weak and their ability to regulate alignment is weak, so sufficient alignment stability There was a problem that could not be obtained. In addition, it is essential to add a polymerization initiator in the polymerization of these polymerizable compounds. If the polymerization initiator is not added, the polymerizable compound remains after the polymerization.

  From the above, the seizure characteristics of the display element, the alignment stability, the stability as a composition that does not cause precipitation, the production efficiency when preparing the PSA type liquid crystal display element, and the like required for the liquid crystal composition containing the polymerizable compound Improvement of characteristics has been strongly desired.

JP 2003-307720 A JP 2008-116931 A JP 2004-302096 A

  The problem to be solved by the present invention is that the polymerizable compound and the liquid crystal material are compatible with each other, the polymerization rate is improved, the orientation after polymerization is more stable, and display characteristics such as image sticking are not caused. An object is to provide a liquid crystal composition containing a functional compound. Furthermore, it is providing the liquid crystal display element which the liquid crystal aligning ability was provided by polymerizing the polymeric compound containing liquid crystal composition, and was excellent in display performance.

  As a result of studying various polymerizable compounds and various non-polymerizable liquid crystal materials, the inventors of the present application have found that a liquid crystal containing a polymerizable compound having a specific structure and a polymerizable compound composed of a non-polymerizable liquid crystal material. The inventors have found that the composition can solve the above-mentioned problems and have completed the present invention.

  That is, as the first component, one or more compounds represented by General Formula (Ia) and one or more compounds represented by General Formula (Ib)

(Wherein R ¹¹ , R ¹³ and R ¹⁴ are the following formulas (R-1) to (R-15)

Any one of
S ¹¹ , S ¹³ and S ¹⁴ represent an alkylene group having 1 to 12 carbon atoms or a single bond, and the methylene group in the alkylene group is an oxygen atom, —COO—, -OCO-, or -OCOO- may be substituted,
Z ¹¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a difluoromethoxy group, or an alkyl group having 1 to 12 carbon atoms, The methylene group is substituted with an oxygen atom, a sulfur atom, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C—, as oxygen atoms are not directly bonded to each other. Or Z ¹¹ may be -S ¹² -R ¹²
(Wherein R ¹² independently represents the same meaning as R ^11, and S ¹² independently represents the same meaning as S ¹¹ ),
X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ , X ²⁰ , X ²¹ and X ²² are each independently a hydrogen atom, an alkyl group, or an alkyl halide. A group, an alkoxy group, a halogenated alkoxy group, a halogen, a cyano group, or a nitro group;
L ¹¹ , L ¹² , L ¹⁴ , L ¹⁵ and L ¹⁶ are each independently a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO. _{-, - C 2 H 4 -} , - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - CO-NR a -, - NR a -CO -, - SCH 2 -, - CH 2 S -, - CH = CH- COO -, - COO-CH = CH -, - OCO-CH = CH -, - CH = CH-OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - _{, - - C 2 H 4 OCO} C 2 H 4 COO -, - OCOCH 2 -, - CH 2 COO -, - CH = CH -, - CF = CH -, - CH = CF -, - CF 2 -, - _{CF 2 O -, - OCF 2} -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 C ₂ - or represents -C≡C-, (wherein, ^{R a} represents an alkyl group having 1 to 4 carbon atoms.)
L ¹³ represents —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH— or —OCO—CH═CH—,
M ¹¹ and M ¹² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, piperidine-2,5. - diyl group, naphthalene-2,6-diyl group, indan-2,5-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl ^{group, M 11} and M ¹² is independently independent of each other or a hydrogen atom contained in these groups is a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group, or a halogenated group. May be substituted with an alkoxy group, an alkoxy group, or a nitro group,
m represents 0 or 1, n represents 1, 2 or 3, m + n represents 1, 2 or 3, and when n represents 2 or 3, 2 or 3 M ¹² and / or L ¹⁴ may be the same or different. ) And a second component as a general formula (II)

(In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one methylene group or an adjacent group present in these groups) Two or more methylene groups which are not present may be substituted with —O— or —S—, and one or more hydrogen atoms present in these groups are substituted with fluorine atoms or chlorine atoms. It ’s okay,
M ²¹ , M ²² and M ²³ are each independently (a) a trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other is -O- or -S- may be substituted),
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by a nitrogen atom), 3-fluoro-1 , 4-phenylene group, 3,5-difluoro-1,4-phenylene group and (c) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-2, A group selected from the group consisting of a 5-diyl group, a naphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group; Represent,
o represents 0, 1 or 2;
L ²¹ and L ²² are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —CH═CH—, —CH═N—N═CH— or —C≡C— is represented, and when there are a plurality of L ²² and / or M ²³ , they may be the same or different. 1) or two or more compounds represented by formula (III), and the general formula (IIIa), general formula (IIIb) and general formula (IIIc) are used as the third component.

(Wherein R ³¹ , R ³² and R ³³ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one methylene group present in these groups) Alternatively, two or more methylene groups that are not adjacent to each other may be substituted with -O- or -S-, and one or more hydrogen atoms present in these groups may be replaced with a fluorine atom or a chlorine atom. May be replaced,
M ³¹ , M ³² , M ³³ , M ³⁴ , M ³⁵ , M ³⁶ , M ³⁷ and M ³⁸ are independent of each other,
(D) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by —O— or —S—). ),
(E) 1,4-phenylene group (one —CH═ present in the group or two or more —CH═ not adjacent to each other may be replaced by a nitrogen atom), 3-fluoro-1 , 4-phenylene group, 3,5-difluoro-1,4-phenylene group,
(F) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group are selected from the group consisting of the above group (d), group (e) or group (f). Each hydrogen atom contained may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ , L ³⁷ and L ³⁸ are each independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH _{2 ) 4 -, - OCH 2 -} , - CH 2 O -, - OCF 2 -, - CF 2 O- or represents ^{-C≡C-, M 32, M 34,} M 35, M 37, M 38, L ^When there are a plurality of ³¹ , L ³³ , L ³⁵ , L ³⁶ and / or L ³⁸ , they may be the same or different,
X ³¹ , X ³² , X ³³ , X ³⁴ , X ³⁵ , X ³⁶ and X ³⁷ each independently represent a hydrogen atom or a fluorine atom,
Y ³¹ , Y ³² and Y ³³ are each independently a hydrogen atom, fluorine atom, chlorine atom, cyano group, thiocyanato group, trifluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethyl group or difluoro. Represents a methoxy group,
At least one of X ³¹ , X ^{32 and} Y ³¹ is a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, or a difluoromethoxy group. Or at least one of the hydrogen atoms contained in M ³¹ or M ³² represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, or a chlorine atom,
At least one of X ³³ , X ³⁴ , X ³⁵ or Y ³² is fluorine atom, chlorine atom, cyano group, thiocyanato group, trifluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethyl group, difluoro Represents a methoxy group, or at least one of hydrogen atoms contained in M ³³ , M ³⁴ or M ³⁵ represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
At least one of X ³⁶ , X ^{37 and} Y ³³ is a fluorine atom, chlorine atom, cyano group, thiocyanato group, trifluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethyl group, difluoromethoxy group. Or at least one of hydrogen atoms contained in M ³⁶ , M ³⁷ and M ³⁸ represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
p, q, r, s and t each independently represent 0, 1 or 2, but q + r and s + t are 2 or less. Or a compound selected from the group consisting of compounds represented by formula (IVa), general formula (IVb) and general formula (IVc)

(Wherein R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and One methylene group present in the group or two or more methylene groups not adjacent to each other may be substituted with -O- or -S-, and one or two present in these groups The above hydrogen atoms may be substituted with fluorine atoms or chlorine atoms,
M ⁴¹ , M ⁴² , M ⁴³ , M ⁴⁴ , M ⁴⁵ , M ⁴⁶ , M ⁴⁷ , M ⁴⁸ and M ⁴⁹ are independent of each other,
(D) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by —O— or —S—). ),
(E) a 1,4-phenylene group (one —CH═ present in the group or two or more —CH═ not adjacent to each other may be replaced by a nitrogen atom);
(F) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group are selected from the group consisting of the above group (d), group (e) or group (f). Each hydrogen atom contained may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁴⁷ , L ⁴⁸ and L ⁴⁹ are each independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O— or —C≡C— represents M ⁴² , M ⁴³ , M ⁴⁵ , M ⁴⁶ , M ⁴⁸ , M ⁴⁹ , L ⁴¹ , L ⁴³ , L ⁴⁴ , L ⁴⁶ , L ⁴⁷ and / or a plurality of L ⁴⁹ , they may be the same or different,
^{X 41, X 42, X 43} , X 44, X 45, X 46, X 47 and ^{X 48} are independently of one another, are a hydrogen atom, a trifluoromethyl group, represents a trifluoromethoxy group or a fluorine ^{atom, X 41} and any one of X ⁴² represents a fluorine ^atom, one of X ^{43, X 44} and ^{X 45} represents a fluorine ^atom, one of X ^{46, X 47} and ^{X 48} represents a fluorine atom However, X ⁴⁶ and X ⁴⁷ do not represent a fluorine atom at the same time, and X ⁴⁶ and X ⁴⁸ do not represent a fluorine atom at the same time.
G represents a methylene group or —O—;
u, v, w, x, y and z each independently represent 0, 1 or 2, but u + v, w + x and y + z are 2 or less. And a polymerizable compound-containing liquid crystal composition characterized by containing one or more compounds selected from the group consisting of compounds represented by formula (1), and a liquid crystal display device using the liquid crystal composition. provide.

  Since the polymerizable compound which is an essential component of the present invention has excellent compatibility with other non-polymerizable liquid crystal materials, a stable liquid crystal composition can be obtained. Further, since it has a skeleton similar to a liquid crystal compound, the alignment regulating power of the liquid crystal compound is strong. In addition, the liquid crystal composition containing the polymerizable compound can polymerize the polymerizable compound without using a photopolymerization initiator or with a very small amount of addition, has a high polymerization rate, and remains unpolymerized after polymerization. There are no or very few polymerizable compounds. In addition, the energy required for polymerization of the polymerizable compound can be greatly reduced. As a result, the display defects of the liquid crystal display element to which orientation is imparted by polymerizing the polymerizable compound in the liquid crystal material can be greatly reduced, and the energy cost for production can be reduced and the production efficiency can be improved. It is useful as a liquid crystal material for liquid crystal display elements.

The polymerizable compound used in the liquid crystal composition containing the polymerizable compound of the present invention is composed of compounds represented by general formula (Ia) and general formula (Ib). In the general formula (Ia) and the general formula (Ib), Z ¹¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a difluoromethoxy group, or a methylene group. Number of carbon atoms that may be substituted with oxygen atoms, sulfur atoms, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C— as atoms that are not directly bonded to each other 1 to 12 alkyl groups or —S ¹² —R ¹² is preferable, and a hydrogen atom, a fluorine atom, or a methylene group is an oxygen atom, —CO—, —COO—, —OCO—, or substituted alkyl group having 1 to 12 carbon atoms in -OCO-, or ^-S 12 ^{-R 12} are more preferable, and a methylene group is not bonded to each other oxygen atom is directly Is substituted with an oxygen atom alkyl group having 1 to 12 carbon atoms, or ^-S 12 ^{-R 12} are more preferred as.

R ¹¹ , R ¹² , R ^13, and R ¹⁴ each represent a polymerizable group, and specific examples of the polymerizable group include the structures shown below.

  These polymerizable groups are cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when performing ultraviolet polymerization as a polymerization method, the formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), formula (R -11), formula (R-13) or formula (R-15) are preferred, and formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula ( R-13) is more preferred, and formula (R-1) or formula (R-2) is more preferred.

S ¹¹ , S ¹² , S ¹³ and S ¹⁴ represent a spacer group or a single bond, and the spacer group is preferably an alkylene group having 1 to 12 carbon atoms or a single bond, and a methylene group in the alkylene group. May be replaced with oxygen atoms, —COO—, —OCO—, or —OCOO— as those in which oxygen atoms are not directly bonded to each other, and the spacer length may be shortened in order to increase the alignment regulating power of the liquid crystal material. Preferably, the upper limit of the number of carbon atoms is preferably 6, preferably 4 is preferable, 3 is preferable, 2 is preferable, 1 is preferable, and a single bond is preferable.

R ¹² independently represents the same meaning as R ^11, and S ¹² independently represents the same meaning as S ¹¹ . When Z ¹¹ is —S ¹² —R ¹² , S ¹¹ and S ¹² each independently represent a spacer group or a single bond, and the spacer group is an alkylene group having 2 to 12 carbon atoms. Or a single bond is preferable, and a methylene group is an alkylene group having 2 to 12 carbon atoms which may be replaced by an oxygen atom, -COO-, -OCO-, or -OCOO- as a group in which oxygen atoms are not directly bonded to each other, Alternatively, a single bond is preferable, and at least one of the methylene groups has 2 to 12 carbon atoms which may be replaced with an oxygen atom, —COO—, —OCO—, or —OCOO—, as oxygen atoms are not directly bonded to each other. An alkylene group is more preferred.

X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ , X ²⁰ , X ²¹ and X ²² are each independently a hydrogen atom, an alkyl group, or an alkyl halide. Group, alkoxy group, halogenated alkoxy group, halogen, cyano group, or nitro group are preferable, hydrogen atom, alkyl group, halogenated alkyl group, alkoxy group, halogenated alkoxy group, or halogen is more preferable, hydrogen atom, alkyl A group, an alkoxy group, or a halogen is more preferable.

L ¹¹ , L ¹² , L ¹⁴ , L ¹⁵ and L ¹⁶ are each independently a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO. _{-, - C 2 H 4 -} , - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - CO-NR a -, - NR a -CO -, - SCH 2 -, - CH 2 S -, - CH = CH- COO -, - COO-CH = CH -, - OCO-CH = CH-OCO -, - CH = CH -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - _{, - - C 2 H 4 OCO} C 2 H 4 COO -, - OCOCH 2 -, - CH 2 COO -, - CH = CH -, - CF = CH -, - CH = CF -, - CF 2 -, - _{CF 2 O -, - OCF 2} -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 C ₂ - or -C≡C- are preferred (wherein, ^{R a} represents an alkyl group having 1 to 4 carbon atoms.), A single bond, -O -, _- OCH 2 -, - _CH 2 O -, - _{CO -, - C 2 H 4} -, - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - CH = CH-COO -, - COO-CH = CH -, - OCO-CH = _{CH-OCO -, - COOC 2} H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - OCOCH 2 -, - CH 2 COO-, or -CH = CH- is more preferably a single _{bond, -O -, - OCH 2 -} , - CH 2 O -, - CH = CH-COO -, - COO-CH = CH -, - OCO-CH = CH-OCO-, _{-COOC 2 H 4 -, - OCOC} 2 H 4 -, - C 2 H 4 OCO -, - _{2 H 4 COO -, - OCOCH} 2 -, - CH 2 COO-, or -CH = CH- is more preferable.

L ¹³ is preferably —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH— or —OCO—CH═CH—, and —CH═CH—COO— or —OCO—CH. = CH- is more preferred. Since these have π electrons, they increase the absorbance of the molecules, and also act as polymerizable groups.

M ¹¹ and M ¹² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, piperidine-2,5- A diyl group, naphthalene-2,6-diyl group, indane-2,5-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group is preferred, and 1,4- A phenylene group, a 1,4-cyclohexylene group, a naphthalene-2,6-diyl group or a tetrahydronaphthalene-2,6-diyl group is more preferable, and a 1,4-phenylene group or a 1,4-cyclohexylene group is particularly preferable. . In M ¹¹ and M ¹² , hydrogen atoms contained in these groups are each independently a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group, a halogenated alkoxy group, an alkoxy group. Group, substituted with a nitro group, or preferably unsubstituted, more preferably substituted with a fluorine atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, or unsubstituted, It is particularly preferable that the fluorine atom is substituted or unsubstituted, and in order to improve the polymerization rate, M ¹¹ and M ¹² in the compound represented by the general formula (Ia) are aromatic ring structures. Preferably there is.

m represents 0 or 1, and n represents 1, 2 or 3. When n represents 2 or 3, two or three M ¹² and / or L ¹⁴ may be the same or different, and m + n is preferably 1, 2 or 3, and importance is attached to solubility. In this case, m + n is preferably 1 or 2.

  More specifically, the compounds represented by the general formula (Ia) are preferably compounds represented by the following general formulas (Ia-1) to (Ia-35).

  Furthermore, the compounds represented by the general formulas (Ia-1) to (Ia-30) are preferable.

  More specifically, the compounds represented by the general formula (Ib) are preferably compounds represented by the following general formulas (Ib-1) to (Ib-38).

Furthermore, the compounds represented by the general formulas (Ib to 1) to (Ib to 34) are preferable.

  In the polymerizable compound-containing liquid crystal composition of the present invention, each of the polymerizable compounds represented by the general formula (Ia) and the general formula (Ib) contains at least one type, but each contains one to five types. It is particularly preferable to contain 1 to 3 types each. If the content of the compounds represented by the general formula (Ia) and the general formula (Ib) is small, the alignment regulating force on the non-polymerizable liquid crystal compound is weakened. Therefore, the lower limit value of the general formula (Ia) is preferably 0.01% by mass, and the lower limit value of the general formula (Ib) is 0.05% by mass. The upper limit of the total sum of general formula (Ia) and general formula (Ib) is preferably 2.0% by mass, and more preferably 1.0% by mass. The proportion of the polymerizable compound represented by the general formula (Ia) and the polymerizable compound represented by the general formula (Ib) in the first component is expressed by the general formula (Ia) when the polymerization rate is important. The represented polymerizable compound is preferably 5% by mass or more, and more preferably 10% by mass or more.

In the compound represented by the general formula (II) used as the second component, R ²¹ and R ²² are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms (these One methylene group present in a group or two or more methylene groups not adjacent to each other is substituted with -O- or -S-, and one or more methylene groups present in these groups The hydrogen atom includes those substituted with a fluorine atom or a chlorine atom.), Preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or An alkenyloxy group having 3 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is particularly preferable.

M ²¹ , M ²² and M ²³ are each independently a trans-1,4-cyclohexylene group (one CH ₂ group present in this group or _two non-adjacent CH ₂ groups are oxygen atoms). Including a substituted group), a 1,4-phenylene group (including one or more CH groups present in this group substituted with a nitrogen atom), 3-fluoro-1, 4-phenylene group, 3,5-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group A naphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, preferably a trans-1,4-cyclohexylene group 1,4-phenyle Group, or 1,4-bicyclo [2.2.2] are more preferred octylene group, trans-1,4-cyclohexylene group or 1,4-phenylene group it is particularly preferred. o is preferably 0, 1 or 2, and more preferably 0 or 1. L ²¹ and L ²² are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—. , —CH═CH—, —CH═N—N═CH— or —C≡C— are preferred, and a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ — or —CH. ₂ O— is more preferable, and a single bond or —CH ₂ CH ₂ — is still more preferable.

  Of the structures formed by combinations of the above options, —CH═CH—CH═CH—, —C≡C—C≡C— and —CH═CH—C≡C— are preferred from the viewpoint of chemical stability. Absent. Similarly, those in which hydrogen atoms in these structures are replaced by fluorine atoms are also not preferable. Similarly, a structure in which oxygens are combined, a structure in which sulfur atoms are combined, and a structure in which sulfur atoms and oxygen atoms are combined are also not preferable. Similarly, a structure in which nitrogen atoms are bonded to each other, a structure in which nitrogen atoms and oxygen atoms are bonded, and a structure in which nitrogen atoms and sulfur atoms are bonded are also not preferable.

  More specifically, the general formula (II) is preferably a compound represented by the following general formula (II-A) to general formula (II-P) as a specific structure.

(Wherein R ²³ and R ²⁴ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 3 to 10 carbon atoms) Represents a group.)
R ²³ and R ²⁴ are each independently preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or More preferred are alkoxy groups having 1 to 10 carbon atoms.

  Among the compounds represented by general formula (II-A) to general formula (II-P), general formula (II-A), general formula (II-B), general formula (II-C), and general formula (II) -E), general formula (II-H), general formula (II-I), general formula (II-I) or a compound represented by general formula (II-K) is preferred, and general formula (II-A) The compound represented by formula (II-C), formula (II-E), formula (II-H) or formula (II-I) is more preferable.

  In the present invention, it contains at least one compound represented by the general formula (II), preferably 1 to 10 types, more preferably 2 to 8 types, and most preferably the general formula (II). Is preferably 5% by mass, more preferably 10% by mass, still more preferably 20% by mass, and particularly preferably 30% by mass. The upper limit is preferably 80% by mass, more preferably 70% by mass, and still more preferably 60% by mass.

In the compounds represented by the general formula (IIIa), general formula (IIIb) and general formula (IIIc) used as the third component, R ³¹ , R ³² and R ³³ are each independently of 1 to 10 carbon atoms. An alkyl group or an alkenyl group having 2 to 10 carbon atoms, a linear alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms (one methylene group present in these groups or adjacent thereto). Two or more methylene groups not substituted by —O— or —S—, and one or more hydrogen atoms present in these groups are substituted by fluorine atoms or chlorine atoms A linear alkyl group having 1 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, more preferably a straight chain having 1 to 8 carbon atoms. Chain alkyl group Or a C1-C8 alkoxy group is especially preferable.

M ³¹ , M ³² , M ³³ , M ³⁴ , M ³⁵ , M ³⁶ , M ³⁷ and M ³⁸ are each independently a trans-1,4-cyclohexylene group (one methylene present in this group). A group or two or more methylene groups not adjacent to each other include those in which -O- or -S- is substituted.), 1,4-phenylene group (one -CH = present in this group) Or two or more non-adjacent —CH═ are substituted with a nitrogen atom), 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine Groups represented by -1,4-diyl group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group (each Each group has a hydrogen atom , A fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, or a group substituted with a chlorine atom.), Trans-1,4-cyclohexylene group, 1,4-phenylene group, 3-fluoro -1,4-phenylene group or 3,5-difluoro-1,4-phenylene group is more preferable, trans-1,4-cyclohexylene group or 1,4-phenylene group is more preferable, and trans-1,4 A cyclohexylene group is particularly preferred.

L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ , L ³⁷ and L ³⁸ are each independently a single bond, —OCO—, —COO—, —CH ₂ CH ₂ —, — (CH _{2 ) 4 -, - OCH 2 -} , - CH 2 O -, - OCF 2 -, - CF 2 O- or -C≡C-, more preferably a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -Or -C≡C- is more preferable, and a single bond or -CH ₂ CH ₂ -is particularly preferable. X ³¹ , X ³² , X ³³ , X ³⁴ , X ³⁵ , X ³⁶ , and X ³⁷ are each independently a hydrogen atom or a fluorine atom, and Y ³¹ , Y ³² , and Y ³³ are each independently a hydrogen atom. Represents a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a difluoromethoxy group, or an alkyl group having 1 to 12 carbon atoms. And preferably represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group or an alkyl group having 1 to 12 carbon atoms. And particularly preferably represents a fluorine atom. p, q, r, s, and t each independently represent 0, 1 or 2, but q + r and s + t represent 2 or less.

  Of the structures formed by combinations of the above options, —CH═CH—CH═CH—, —C≡C—C≡C— and —CH═CH—C≡C— are preferred from the viewpoint of chemical stability. Absent. Similarly, those in which hydrogen atoms in these structures are replaced by fluorine atoms are also not preferable. Similarly, a structure in which oxygens are combined, a structure in which sulfur atoms are combined, and a structure in which sulfur atoms and oxygen atoms are combined are also not preferable. Similarly, a structure in which nitrogen atoms are bonded to each other, a structure in which nitrogen atoms and oxygen atoms are bonded, and a structure in which nitrogen atoms and sulfur atoms are bonded are also not preferable.

  Specifically, it is preferable to represent a structure represented by the following general formula (IIIa-1).

(In the formula, R ³⁴ represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, and L ³⁹ and L ⁴⁰ are each independently a single atom. M ³⁸ represents a bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O— or —C≡C—. represents a 1,4-phenylene group or a trans-1,4-cyclohexylene ^{group, X 32} represents a hydrogen atom or a fluorine atom, _{p 1} represents 0 or ^{1, Y 34} is a cyano group, a fluorine atom, a chlorine atom Represents a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group.)
More specifically, the following general formulas (IIIa-2a) to (IIIa-4d)

(In the formula, R ³⁴ represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, and X ³¹ and X ³² are each independently hydrogen. Y ³¹ represents a cyano group, a fluorine atom, a chlorine atom, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, or a trifluoromethoxy group.

(In the formula, R ³⁴ represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and Y ³¹ represents a cyano group, a fluorine atom, or a chlorine atom. Represents a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, or a trifluoromethoxy group).

  General formula (IIIb) has the following general formula as a specific structure:

(In the formula, R ³⁵ represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and Y ³⁵ represents a cyano group, a fluorine atom, or a chlorine atom. Represents a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group).
General formula (IIIc) has the following general formula as a specific structure:

(In the formula, R ³⁶ represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and Y ³⁶ represents a cyano group, a fluorine atom, or a chlorine atom. Represents a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group.

  It contains at least one compound selected from the group consisting of compounds represented by general formula (IIIa), general formula (IIIb) and general formula (IIIc), preferably 1 to 10 types. It is particularly preferable to contain 8 to 8 species, and the lower limit of the content of the group consisting of the compounds represented by the general formula (IIIa), general formula (IIIb) and general formula (IIIc) is 5% by mass. Preferably, it is 10% by mass, more preferably 20% by mass, and the upper limit is preferably 80% by mass, preferably 70% by mass, preferably 60% by mass, and further preferably 50% by mass.

In the compounds represented by general formula (IVa), general formula (IVb) and general formula (IVc), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are each independently a carbon atom. An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a linear alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms (one methylene present in these groups) A group or two or more methylene groups not adjacent to each other are substituted by —O— or —S—, and one or more hydrogen atoms present in these groups are fluorine atoms or chlorine atoms In addition, a linear alkyl group having 1 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms is more preferable. 1-8 linear al A kill group or an alkoxy group having 1 to 8 carbon atoms is particularly preferred. M ⁴¹ , M ⁴² , M ⁴³ , M ⁴⁴ , M ⁴⁵ , M ⁴⁶ , M ⁴⁷ , M ⁴⁸ and M ⁴⁹ are independently of each other a trans-1,4-cyclohexylene group (1 present in this group). A methylene group or two or more methylene groups which are not adjacent to each other include those in which -O- or -S- is substituted.), A 1,4-phenylene group (one in this group) -CH = or two or more non-adjacent -CH = include those substituted with a nitrogen atom), 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene Group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group Groups (hydrogen atoms in each group Are preferably substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom.), Trans-1,4-cyclohexylene group, 1,4-phenylene group 3-fluoro-1,4-phenylene group or 2,3-difluoro-1,4-phenylene group is more preferable, trans-1,4-cyclohexylene group or 1,4-phenylene group is more preferable, and trans A -1,4-cyclohexylene group is particularly preferred. L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁴⁷ , L ⁴⁸ and L ⁴⁹ are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, — _{OCO -, - COO -, -} OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O- or -C≡C-, more preferably a single _{bond, -CH 2 CH 2 -, -} OCH 2 - or _-CH 2 O-are more preferred. X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , and X ⁴⁷ each independently represent a hydrogen atom or a fluorine atom, G represents a methylene group or —O—, u, v, w , X, y and z each independently represent 0, 1 or 2, but u + v, w + x and y + z are each represented by 2 or less.

  In the compound represented by the general formula (IVa), specifically, a structure represented by the following general formula (IVa-1) is preferably represented.

(Wherein R ⁴⁷ and R ⁴⁸ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, L ⁵⁰ , L ⁵¹ and L ⁵² are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O— or — C≡C—, M ⁵⁰ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and u ₁ and v ₁ each independently represents 0 or 1.)
Of the structures formed by combinations of the above options, —CH═CH—CH═CH—, —C≡C—C≡C— and —CH═CH—C≡C— are preferred from the viewpoint of chemical stability. Absent. Similarly, those in which hydrogen atoms in these structures are replaced by fluorine atoms are also not preferable. Similarly, a structure in which oxygens are combined, a structure in which sulfur atoms are combined, and a structure in which sulfur atoms and oxygen atoms are combined are also not preferable. Similarly, a structure in which nitrogen atoms are bonded to each other, a structure in which nitrogen atoms and oxygen atoms are bonded, and a structure in which nitrogen atoms and sulfur atoms are bonded are also not preferable.

  More specifically, the following general formula (IVa-2a) to general formula (IVa-3i)

(Wherein R ⁴⁷ and R ⁴⁸ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms). In which R ⁴⁷ and R ⁴⁸ are each independently an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

  In the compound represented by the general formula (IVb), specifically, it is preferable to represent a structure represented by the following general formula (IVb-1).

(In the formula, R ⁴⁹ and R ⁵⁰ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, L ⁵² , L ⁵³ and L ⁵⁴ are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O— or — C≡C—, M ⁵¹ , M ⁵² and M ⁵³ represent 1,4-phenylene group or trans-1,4-cyclohexylene group, and w1 and x1 independently represent 0, 1 or 2. However, w1 + x1 represents 2 or less.)
More specifically, the following general formulas (IVb-2a) to (IVb-3l)

(Wherein R ⁴⁹ and R ⁵⁰ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms). The structure is preferred.

  In the compound represented by the general formula (IVc), specifically, it is preferable to represent a structure represented by the following general formula (IVc-1a) and general formula (IVc-1b).

(Wherein R ⁵¹ and R ⁵² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, L ⁵⁶ , L ⁵⁷ and L ⁵⁸ are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O— or — C≡C—, M ⁵⁴ , M ⁵⁵ and M ^{56 each} represent a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and y 1 and z 1 each independently represent 0, 1 or 2. However, y1 + z1 represents 2 or less.)
More specifically, the following general formulas (IVc-2a) to (IVc-2g)

(In the formula, R ⁵¹ and R ⁵² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms.)
A compound selected from the group consisting of compounds represented by general formula (IIIa), general formula (IIIb) and general formula (IIIc) used as the third component, or general formula (IVa), general formula (IVb) and general It contains at least one compound selected from the group consisting of compounds represented by formula (IVc), but preferably contains 2 to 10 species, particularly preferably 2 to 8 species, and the content rate The lower limit is preferably 5% by mass, more preferably 10% by mass, more preferably 20% by mass, and the upper limit is preferably 80% by mass, and is 70% by mass. It is preferably 60% by mass, and preferably 50% by mass.

  In the liquid crystal composition of the present invention, Δn is preferably in the range of 0.08 to 0.25.

  In the liquid crystal composition of the present invention, Δε having a positive or negative Δε can be used depending on the display mode of the liquid crystal display element. In the MVA mode liquid crystal display element, a liquid crystal composition having a negative Δε is used. In that case, Δε is preferably −1 or less, and more preferably −2 or less.

  The liquid crystal composition of the present invention has a wide liquid crystal phase temperature range (absolute value of the difference between the liquid crystal phase lower limit temperature and the liquid crystal phase upper limit temperature), but the liquid crystal phase temperature range is preferably 100 ° C or higher, and 120 ° C or higher. Is more preferable. The upper limit temperature of the liquid crystal phase is preferably 70 ° C. or higher, and more preferably 80 ° C. or higher. Furthermore, the lower limit temperature of the liquid crystal phase is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower.

  The liquid crystal composition of the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal and the like in addition to the above compounds.

  The liquid crystal composition containing the polymerizable compound of the present invention is polymerized even when no polymerization initiator is present, but may contain a polymerization initiator in order to accelerate the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, and the like.

  In order to improve the storage stability of the liquid crystal composition of the present invention, a stabilizer may be added. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. The addition amount in the case of using a stabilizer is preferably in the range of 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass, and 0.03 to 0.1% by mass with respect to the liquid crystal composition. % Is particularly preferred.

  The liquid crystal composition of the present invention is used for a liquid crystal display element that is provided with liquid crystal alignment ability by polymerization of a polymerizable compound in the liquid crystal composition and controls the amount of light transmitted using the birefringence of the liquid crystal composition. Is done. As liquid crystal display elements, AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD and IPS-LCD (in-plane switching liquid crystal display element) However, it is particularly useful for AM-LCDs, and can be used for transmissive or reflective liquid crystal display elements.

  The two substrates of the liquid crystal cell used in the liquid crystal display element can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon. A transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.

  The color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.

  The said board | substrate is made to oppose so that a transparent electrode layer may become an inner side. In that case, you may adjust the space | interval of a board | substrate through a spacer. At this time, it is preferable to adjust so that the thickness of the light control layer obtained may be set to 1-100 micrometers. More preferably, the thickness is 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist material. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.

  As a method for sandwiching the polymer-stabilized liquid crystal composition between the two substrates, a normal vacuum injection method, an ODF method, or the like can be used.

  As a method for polymerizing a polymerizable compound, since rapid progress of polymerization is desirable, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask during light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating current to the polymerizable compound-containing liquid crystal composition. The alternating current to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the MVA mode liquid crystal display element, it is preferable to control the pretilt angle from 80 degrees to 89 degrees from the viewpoint of alignment stability and contrast.

The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. Polymerization is preferably performed at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet-rays to irradiate, it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a liquid crystal composition, and it is preferable to cut and use an ultraviolet-ray as needed. Intensity of ultraviolet irradiation is ^preferably from ^{0.1mW / cm 2 ~100W / cm 2} , 2mW / cm 2 ~50W / cm 2 is more preferable. Energy of ultraviolet light irradiation, can be appropriately ^adjusted, preferably ^{1mJ / cm 2 ~500J / cm 2} , 100mJ / cm 2 ~200J / cm 2 is more preferable. When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiating ultraviolet rays, but is preferably 10 seconds to 3600 seconds.

  EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.

The physical properties of the liquid crystal composition are expressed as follows.
T _N-I (° C.): Nematic phase-isotropic liquid phase transition temperature (liquid crystal phase upper limit temperature)
Δε: dielectric anisotropy Δn: refractive index anisotropy Vth (V): applied voltage (threshold voltage) at which the transmittance changes by 10% when a rectangular wave having a frequency of 1 kHz is applied
(Measurement method of residual amount of monomer after UV curing)
After injecting the liquid crystal composition into the liquid crystal cell, UV is irradiated to polymerize the polymerizable compound. Thereafter, the liquid crystal cell is disassembled to obtain an acetonitrile solution of an elution component containing a liquid crystal material, a polymer, and an unpolymerized polymerizable compound. The peak area of each component is measured by high performance liquid chromatography (detector: UV, column: reverse phase nonpolar column, developing solvent: acetonitrile). The amount of the remaining polymerizable compound was determined from the peak area ratio of the liquid crystal material as an index and the peak area ratio of the unpolymerized polymerizable compound. The residual monomer amount was determined from this value and the amount of the polymerizable compound initially added. The detection limit of the remaining amount of the polymerizable compound was 100 ppm.
Example 1
A compound selected from general formula (II), a compound selected from general formula (IIIa), general formula (IIIb) and general formula (IIIc), or general formula (IVa), general formula (IVb) and general formula (IVc) A liquid crystal composition LC-1 containing a compound selected from: The constituent compounds and the ratios contained are as follows.

  Table 1 shows the physical properties of the liquid crystal composition LC-1.

  For the liquid crystal composition LC-1 99.6%,

A polymerizable liquid crystal composition is prepared by adding 0.05% of the polymerizable compound represented by the general formula (Ia-2) and adding 0.35% of the polymerizable compound represented by the general formula (Ib-1) and uniformly dissolving it. The product CLC-1 was prepared. The physical properties of CLC-1 were almost the same as the physical properties of LC-1. For this reason, it turned out that the polymeric compound represented by general formula (Ia-2) and general formula (Ib-1) does not reduce the liquid crystallinity of the liquid crystal composition to add. Further, although this CLC-1 was stored in a cold place (−20 ° C.) for 1 week, precipitation or the like did not occur, and the polymerizable compounds represented by the general formula (Ia-2) and the general formula (Ib-1) It was found that the compatibility with the liquid crystal compound was excellent. CLC-1 was injected by a vacuum injection method into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle (crystal rotation method) of this cell, the liquid crystal cell is irradiated with ultraviolet light by a high-pressure mercury lamp through a filter that cuts ultraviolet light of 300 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 kHz. did. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. Table 2 shows the pretilt angle of the element before and after UV irradiation and the electro-optical characteristics of the element.

  From the result of the above pretilt angle, the polymerizable compound is polymerized to cause alignment regulating force on the liquid crystal compound, and the vertical alignment in which the pretilt angle is fixed while the liquid crystal molecules are tilted 3.5 degrees from the vertical direction. It was found that a liquid crystal display element was obtained.

Moreover, although the content of the compound shown by the general formula (Ia-2) and the general formula (Ib-1) contained in the element was analyzed by liquid chromatographic analysis, it was not detected. As a result, the polymerizable compounds represented by the general formulas (Ia-2) and (Ib-1) can be polymerized without using a polymerization initiator, and unpolymerized substances remaining after the polymerization are detected. It was confirmed that it was below the limit.
(Comparative Example 1)
For the liquid crystal composition LC-1 99.6%, the formula (A)

A polymerizable liquid crystal composition CLC-A was prepared by adding 0.4% of the polymerizable compound represented by the formula (II) and dissolving it uniformly. CLC-A was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of the cell, the liquid crystal cell was irradiated with ultraviolet rays by a high pressure mercury lamp through a filter that cuts ultraviolet rays of 300 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 kHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the device was 89.7 degrees, whereas the pretilt angle after the irradiation was 87.8, and the tilt was small but the liquid crystal molecules were tilted from the vertical direction. Was fixed. As a result of analyzing the content of the compound represented by the general formula (A) contained in the element by liquid chromatographic analysis, the content was slightly decreased as compared with that before the ultraviolet irradiation, and the polymerization of the polymerizable compound (A) Was progressing, but it was found that it was not below the detection limit. For this reason, it turned out that a polymerization rate is slow only with the polymeric compound represented by general formula (A). Further, since this CLC-A was stored in a cold place (−20 ° C.) for 1 week, precipitation occurred, and it was found that only the polymerizable compound represented by the general formula (A) had poor compatibility with the liquid crystal compound. .
(Example 2)
0.04% of the polymerizable compound represented by the general formula (Ia-2) is added to 99.7% of the liquid crystal composition LC-1 and 0% of the polymerizable compound represented by the general formula (Ib-1) is added. Polymeric liquid crystal composition CLC-2 was prepared by adding .26% and dissolving uniformly. CLC-2 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of the cell, the liquid crystal cell was irradiated with ultraviolet rays by a high pressure mercury lamp through a filter that cuts ultraviolet rays of 300 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 kHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.6 degrees, whereas the pretilt angle after the irradiation was 87.4 degrees, and the pretilt angle was fixed while the liquid crystal molecules were tilted from the vertical direction. It was. The content of the compound represented by general formula (Ia-2) and general formula (Ib-1) contained in the device was analyzed by liquid chromatographic analysis, but the content was below the detection limit. As a result, the polymerizable compounds represented by the general formulas (Ia-2) and (Ib-1) can be polymerized without using a polymerization initiator, and unpolymerized substances remaining after the polymerization are detected. It was confirmed that it was below the limit.
(Example 3)
With respect to 99.7% of liquid crystal composition LC-1

A polymerizable liquid crystal composition is obtained by adding 0.04% of the polymerizable compound represented by the general formula (Ia-3) and adding 0.26% of the polymerizable compound represented by the general formula (Ib-3) and uniformly dissolving it. The product CLC-3 was prepared. It was found that the polymerizable compounds represented by the general formulas (Ia-3) and (Ib-3) do not deteriorate the liquid crystal properties of the liquid crystal composition to be added. Further, although this CLC-1 was stored in a cold place (−20 ° C.) for 1 week, precipitation or the like did not occur, and the polymerizable compounds represented by the general formula (Ia-3) and the general formula (Ib-3) It was found that the compatibility with the liquid crystal compound was excellent. CLC-3 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of the cell, the liquid crystal cell was irradiated with ultraviolet rays by a high pressure mercury lamp through a filter that cuts ultraviolet rays of 300 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 kHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the device was 89.6 degrees, whereas the pretilt angle after the irradiation was 87.1 degrees, and the pretilt angle was fixed while the liquid crystal molecules were tilted from the vertical direction. It was. The content of the compound represented by general formula (Ia-3) and general formula (Ib-3) contained in the device was analyzed by liquid chromatographic analysis, but was below the detection limit. As a result, the polymerizable compounds represented by the general formulas (Ia-3) and (Ib-3) can be polymerized without using a polymerization initiator, and unpolymerized substances remaining after the polymerization are detected. It was confirmed that it was below the limit.
Example 4
With respect to 99.8% of liquid crystal composition LC-1

A polymerizable liquid crystal composition is obtained by adding 0.03% of the polymerizable compound represented by the general formula (Ia-1) and adding 0.17% of the polymerizable compound represented by the general formula (Ib-5) and uniformly dissolving it. The product CLC-4 was prepared. It was found that the polymerizable compounds represented by the general formulas (Ia-1) and (Ib-5) do not deteriorate the liquid crystal properties of the liquid crystal composition to be added. Further, although this CLC-1 was stored in a cold place (−20 ° C.) for 1 week, precipitation or the like did not occur, and the polymerizable compounds represented by the general formula (Ia-1) and the general formula (Ib-5) It was found that the compatibility with the liquid crystal compound was excellent. CLC-4 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of the cell, the liquid crystal cell was irradiated with ultraviolet rays by a high pressure mercury lamp through a filter that cuts ultraviolet rays of 300 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 kHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the device was 89.8 degrees, whereas the pretilt angle after the irradiation was 88.1 degrees, and the pretilt angle was fixed while the liquid crystal molecules were tilted from the vertical direction. It was. The content of the compound represented by general formula (Ia-1) and general formula (Ib-5) contained in the device was analyzed by liquid chromatographic analysis, but the content was below the detection limit. As a result, the polymerizable compounds represented by the general formulas (Ia-1) and (Ib-5) can be polymerized without using a polymerization initiator, and unpolymerized substances remaining after the polymerization are detected. It was confirmed that it was below the limit.
(Example 5)
0.02% of the polymerizable compound represented by the general formula (Ia-1) is added to 99.9% of the liquid crystal composition LC-1 and the polymerizable compound represented by the general formula (Ib-5) is 0%. A polymerizable liquid crystal composition CLC-5 was prepared by adding 0.08% and dissolving uniformly. CLC-5 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of the cell, the liquid crystal cell was irradiated with ultraviolet rays by a high pressure mercury lamp through a filter that cuts ultraviolet rays of 300 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 kHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.7 degrees, whereas the pretilt angle after the irradiation was 88.6 degrees, and the pretilt angle was fixed while the liquid crystal molecules were tilted from the vertical direction. It was. The content of the compound represented by general formula (Ia-1) and general formula (Ib-5) contained in the device was analyzed by liquid chromatographic analysis, but the content was below the detection limit. As a result, the polymerizable compounds represented by the general formulas (Ia-1) and (Ib-5) can be polymerized without using a polymerization initiator, and unpolymerized substances remaining after the polymerization are detected. It was confirmed that it was below the limit.
(Example 6)
A compound selected from general formula (II), a compound selected from general formula (IIIa), general formula (IIIb) and general formula (IIIc), or general formula (IVa), general formula (IVb) and general formula (IVc) As an example containing a compound selected from the following, a liquid crystal composition LC-2 having the following components was prepared.

  Table 3 shows the physical properties of the liquid crystal composition LC-2.

0.04% of the polymerizable compound represented by the general formula (Ia-2) is added to 99.7% of the liquid crystal composition LC-2, and the polymerizable compound represented by the general formula (Ib-1) is 0%. Polymeric liquid crystal composition CLC-6 was prepared by adding .26% and uniformly dissolving. It was found that the polymerizable compounds represented by the general formulas (Ia-2) and (Ib-1) do not deteriorate the liquid crystal properties of the liquid crystal composition to be added. Further, although this CLC-1 was stored in a cold place (−20 ° C.) for 1 week, precipitation or the like did not occur, and the polymerizable compounds represented by the general formula (Ia-2) and the general formula (Ib-1) It was found that the compatibility with the liquid crystal compound was excellent. CLC-6 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of the cell, the liquid crystal cell was irradiated with ultraviolet rays by a high pressure mercury lamp through a filter that cuts ultraviolet rays of 300 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 kHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.7 degrees, whereas the pretilt angle after the irradiation was 87.7 degrees, and the pretilt angle was changed with the liquid crystal molecules tilted from the vertical direction. It was fixed. The content of the compound represented by general formula (Ia-2) and general formula (Ib-1) contained in the device was analyzed by liquid chromatographic analysis, but the content was below the detection limit. As a result, the polymerizable compounds represented by the general formulas (Ia-2) and (Ib-1) can be polymerized without using a polymerization initiator, and unpolymerized substances remaining after the polymerization are detected. It was confirmed that it was below the limit.
(Example 7)
A compound selected from general formula (II), a compound selected from general formula (IIIa), general formula (IIIb) and general formula (IIIc), or general formula (IVa), general formula (IVb) and general formula (IVc) As an example containing a compound selected from the following, a liquid crystal composition LC-3 having the following components was prepared.

  Table 4 shows the physical properties of the liquid crystal composition LC-3.

0.04% of the polymerizable compound represented by the general formula (Ia-2) is added to 99.7% of the liquid crystal composition LC-3, and the polymerizable compound represented by the general formula (Ib-1) is 0%. A polymerizable liquid crystal composition CLC-7 was prepared by adding .26% and dissolving uniformly. It was found that the polymerizable compounds represented by the general formulas (Ia-2) and (Ib-1) do not deteriorate the liquid crystal properties of the liquid crystal composition to be added. Further, although this CLC-1 was stored in a cold place (−20 ° C.) for 1 week, precipitation or the like did not occur, and the polymerizable compounds represented by the general formula (Ia-2) and the general formula (Ib-1) It was found that the compatibility with the liquid crystal compound was excellent. CLC-7 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of the cell, the liquid crystal cell was irradiated with ultraviolet rays by a high pressure mercury lamp through a filter that cuts ultraviolet rays of 300 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 kHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.5 degrees, whereas the pretilt angle after the irradiation was 87.6 degrees, and the pretilt angle was 87.6 degrees. It was fixed. The content of the compound represented by general formula (Ia-2) and general formula (Ib-1) contained in the device was analyzed by liquid chromatographic analysis, but the content was below the detection limit. As a result, the polymerizable compounds represented by the general formulas (Ia-2) and (Ib-1) can be polymerized without using a polymerization initiator, and unpolymerized substances remaining after the polymerization are detected. It was confirmed that it was below the limit.
(Example 8)
A compound selected from general formula (II), a compound selected from general formula (IIIa), general formula (IIIb) and general formula (IIIc), or general formula (IVa), general formula (IVb) and general formula (IVc) As an example containing a compound selected from the following, a liquid crystal composition LC-4 having the following components was prepared.

  Table 5 shows the physical properties of the liquid crystal composition LC-4.

0.04% of the polymerizable compound represented by the general formula (Ia-2) is added to 99.7% of the liquid crystal composition LC-4, and the polymerizable compound represented by the general formula (Ib-1) is reduced to 0. Polymeric liquid crystal composition CLC-8 was prepared by adding .26% and dissolving uniformly. It was found that the polymerizable compounds represented by the general formulas (Ia-2) and (Ib-1) do not deteriorate the liquid crystal properties of the liquid crystal composition to be added. Further, although this CLC-1 was stored in a cold place (−20 ° C.) for 1 week, precipitation or the like did not occur, and the polymerizable compounds represented by the general formula (Ia-2) and the general formula (Ib-1) It was found that the compatibility with the liquid crystal compound was excellent. CLC-8 was injected by a vacuum injection method into a cell with ITO coated with a polyimide alignment film that induces parallel alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of the cell, the liquid crystal cell was irradiated with ultraviolet rays by a high pressure mercury lamp through a filter that cuts ultraviolet rays of 300 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 kHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the device was 0.2 degrees, whereas the pretilt angle after irradiation was 3.1 degrees, and the pretilt angle was obtained when the liquid crystal molecules were tilted from the horizontal direction. Was fixed. The content of the compound represented by general formula (Ia-2) and general formula (Ib-1) contained in the device was analyzed by liquid chromatographic analysis, but the content was below the detection limit. As a result, the polymerizable compounds represented by the general formulas (Ia-2) and (Ib-1) can be polymerized without using a polymerization initiator, and unpolymerized substances remaining after the polymerization are detected. It was confirmed that it was below the limit.
(Example 9 and Comparative Example 2)
A voltage was applied to the liquid crystal display elements after polymerization prepared in Examples 1 to 8 and Comparative Example 1, and the elapsed time and the state of image sticking were visually observed. (○ indicates that no change is observed. × indicates burn-in, and the greater the number of ×, the worse the degree.)

  The liquid crystal display device manufactured in Comparative Example 1 burned in 48 hours after display, and display defects were observed over almost the entire surface after 168 hours. On the other hand, in the liquid crystal display element produced in Examples 1-8, the favorable display state was maintained even after 500 hours passed. As a result, it is possible to confirm the high reliability of the liquid crystal display element in which all the polymerizable material is polymerized and consumed, such as the compound of the present invention, and the polymer has sufficiently high rigidity without causing a decrease in the alignment regulating force. I understood it.

Claims (8)

As the first component, one or more compounds represented by general formula (Ia) and one or more compounds represented by general formula (Ib)

(Wherein R ¹¹ , R ¹³ and R ¹⁴ are the following formulas (R-1) to (R-15)

Any one of
S ¹¹ , S ¹³ and S ¹⁴ represent an alkylene group having 1 to 12 carbon atoms or a single bond, and the methylene group in the alkylene group is an oxygen atom, —COO—, -OCO-, or -OCOO- may be substituted,
Z ¹¹ represents -S ¹² -R ¹²
(Wherein R ¹² independently represents the same meaning as R ^11, and S ¹² independently represents the same meaning as S ¹¹ ),
X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ , X ²⁰ , X ²¹ and X ²² are each independently a hydrogen atom, an alkyl group, or an alkyl halide. A group, an alkoxy group, a halogenated alkoxy group, a halogen, a cyano group, or a nitro group;
L ¹¹ , L ¹² , L ¹⁴ , L ¹⁵ and L ¹⁶ are each independently a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO. _{-, - C 2 H 4 -} , - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - CO-NR a -, - NR a -CO -, - SCH 2 -, - CH 2 S -, - CH = CH- COO -, - COO-CH = CH -, - OCO-CH = CH -, - CH = CH-OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - _{, - - C 2 H 4 OCO} C 2 H 4 COO -, - OCOCH 2 -, - CH 2 COO -, - CH = CH -, - CF = CH -, - CH = CF -, - CF 2 -, - _{CF 2 O -, - OCF 2} -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 C ₂ - or represents -C≡C-, (wherein, ^{R a} represents an alkyl group having 1 to 4 carbon atoms.)
L ¹³ represents —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH— or —OCO—CH═CH—,
M ¹¹ and M ¹² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, piperidine-2,5. - diyl group, naphthalene-2,6-diyl group, indan-2,5-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl ^{group, M 11} and M ¹² is independently independent of each other or a hydrogen atom contained in these groups is a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group, or a halogenated group. May be substituted with an alkoxy group, an alkoxy group, or a nitro group,
m represents 0 or 1, n represents 1, 2 or 3, m + n represents 1, 2 or 3, and when n represents 2 or 3, 2 or 3 M ¹² and / or L ¹⁴ may be the same or different. ) And a second component as a general formula (II)

(In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one methylene group or an adjacent group present in these groups) Two or more methylene groups which are not present may be substituted with —O— or —S—, and one or more hydrogen atoms present in these groups are substituted with fluorine atoms or chlorine atoms. It ’s okay,
M ²¹ , M ²² and M ²³ are each independently (a) a trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other is -O- or -S- may be substituted),
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by a nitrogen atom), 3-fluoro-1 , 4-phenylene group, 3,5-difluoro-1,4-phenylene group and (c) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-2, A group selected from the group consisting of a 5-diyl group, a naphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group; Represent,
o represents 0, 1 or 2;
L ²¹ and L ²² are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —CH═CH—, —CH═N—N═CH— or —C≡C— is represented, and when there are a plurality of L ²² and / or M ²³ , they may be the same or different. 1) or two or more compounds represented by formula (III), and the general formula (IIIa), general formula (IIIb) and general formula (IIIc) are used as the third component.

(Wherein R ³¹ , R ³² and R ³³ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one methylene group present in these groups) Alternatively, two or more methylene groups that are not adjacent to each other may be substituted with -O- or -S-, and one or more hydrogen atoms present in these groups may be replaced with a fluorine atom or a chlorine atom. May be replaced,
M ³¹ , M ³² , M ³³ , M ³⁴ , M ³⁵ , M ³⁶ , M ³⁷ and M ³⁸ are independent of each other,
(D) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by —O— or —S—). ),
(E) 1,4-phenylene group (one —CH═ present in the group or two or more —CH═ not adjacent to each other may be replaced by a nitrogen atom), 3-fluoro-1 , 4-phenylene group, 3,5-difluoro-1,4-phenylene group,
(F) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group are selected from the group consisting of the above group (d), group (e) or group (f). Each hydrogen atom contained may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ , L ³⁷ and L ³⁸ are each independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH _{2 ) 4 -, - OCH 2 -} , - CH 2 O -, - OCF 2 -, - CF 2 O- or represents ^{-C≡C-, M 32, M 34,} M 35, M 37, M 38, L ^When there are a plurality of ³¹ , L ³³ , L ³⁵ , L ³⁶ and / or L ³⁸ , they may be the same or different,
X ³¹ , X ³² , X ³³ , X ³⁴ , X ³⁵ , X ³⁶ and X ³⁷ each independently represent a hydrogen atom or a fluorine atom,
Y ³¹ , Y ³² and Y ³³ are each independently a hydrogen atom, fluorine atom, chlorine atom, cyano group, thiocyanato group, trifluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethyl group or difluoro. Represents a methoxy group,
At least one of X ³¹ , X ^{32 and} Y ³¹ is a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, or a difluoromethoxy group. Or at least one of the hydrogen atoms contained in M ³¹ or M ³² represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, or a chlorine atom,
At least one of X ³³ , X ³⁴ , X ³⁵ or Y ³² is fluorine atom, chlorine atom, cyano group, thiocyanato group, trifluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethyl group, difluoro Represents a methoxy group, or at least one of hydrogen atoms contained in M ³³ , M ³⁴ or M ³⁵ represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
At least one of X ³⁶ , X ^{37 and} Y ³³ is a fluorine atom, chlorine atom, cyano group, thiocyanato group, trifluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethyl group, difluoromethoxy group. Or at least one of hydrogen atoms contained in M ³⁶ , M ³⁷ and M ³⁸ represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
p, q, r, s and t each independently represent 0, 1 or 2, but q + r and s + t are 2 or less. Or a compound selected from the group consisting of compounds represented by formula (IVa), general formula (IVb) and general formula (IVc)

(Wherein R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and One methylene group present in the group or two or more methylene groups not adjacent to each other may be substituted with -O- or -S-, and one or two present in these groups The above hydrogen atoms may be substituted with fluorine atoms or chlorine atoms,
M ⁴¹ , M ⁴² , M ⁴³ , M ⁴⁴ , M ⁴⁵ , M ⁴⁶ , M ⁴⁷ , M ⁴⁸ and M ⁴⁹ are independent of each other,
(D) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by —O— or —S—). ),
(E) a 1,4-phenylene group (one —CH═ present in the group or two or more —CH═ not adjacent to each other may be replaced by a nitrogen atom);
(F) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group are selected from the group consisting of the above group (d), group (e) or group (f). Each hydrogen atom contained may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁴⁷ , L ⁴⁸ and L ⁴⁹ are each independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O— or —C≡C— represents M ⁴² , M ⁴³ , M ⁴⁵ , M ⁴⁶ , M ⁴⁸ , M ⁴⁹ , L ⁴¹ , L ⁴³ , L ⁴⁴ , L ⁴⁶ , L ⁴⁷ and / or a plurality of L ⁴⁹ , they may be the same or different,
^{X 41, X 42, X 43} , X 44, X 45, X 46, X 47 and ^{X 48} are independently of one another, are a hydrogen atom, a trifluoromethyl group, represents a trifluoromethoxy group or a fluorine ^{atom, X 41} and any one of X ⁴² represents a fluorine ^atom, one of X ^{43, X 44} and ^{X 45} represents a fluorine ^atom, one of X ^{46, X 47} and ^{X 48} represents a fluorine atom However, X ⁴⁶ and X ⁴⁷ do not represent a fluorine atom at the same time, and X ⁴⁶ and X ⁴⁸ do not represent a fluorine atom at the same time.
G represents a methylene group or —O—;
u, v, w, x, y and z each independently represent 0, 1 or 2, but u + v, w + x and y + z are 2 or less. A polymerizable compound-containing liquid crystal composition containing one or more compounds selected from the group consisting of compounds represented by formula (1): In the general formula (Ia), at least one of S ¹¹ and ^{S 21} are the carbon atoms the oxygen atoms as each other oxygen atoms are not linked directly, -COO -, - OCO-, or may be replaced with -OCOO- The liquid crystal composition according to claim 1, wherein the liquid crystal composition represents an alkylene group having 2 to 12 carbon atoms. The general formula (Ia) and the general formula (Ib), wherein R ¹¹ , R ¹³ and R ¹⁴ each independently represent the formula (R-1) or (R-2). The polymerizable compound-containing liquid crystal composition described. A liquid crystal having a structure in which a liquid crystal is sandwiched between a pair of substrates, having at least a transparent electrode and a polarizing plate, and imparting liquid crystal alignment ability by polymerizing a polymerizable compound contained in the liquid crystal composition. The polymerizable compound-containing liquid crystal composition according to claim 1, which is used for a display element. 0.01 to 2% by mass of the sum of the compounds selected from general formula (Ia) and general formula (Ib), 5 to 70% by mass of the compound selected from general formula (II), general formula (IIIa), A compound selected from the group consisting of compounds represented by general formula (IIIb) or general formula (IIIc) or a group consisting of compounds represented by general formula (IVa), general formula (IVb) and general formula (IVc) The polymerizable compound-containing liquid crystal composition according to any one of claims 1, 2, 3, and 4, wherein the selected compound contains 5 to 70% by mass. 3. The third component contains one or more compounds selected from the group consisting of compounds represented by general formula (IVa), general formula (IVb) and general formula (IVc). The polymerizable compound-containing liquid crystal composition according to any one of 2, 3, 4, or 5. Liquid crystal by polymerizing a polymerizable compound in the polymerizable compound-containing liquid crystal composition using the polymerizable compound-containing liquid crystal composition according to any one of claims 1, 2, 3, 4, 5 or 6. A liquid crystal display element characterized by imparting alignment ability. The liquid crystal display element according to claim 7, wherein the dielectric anisotropy of the polymerizable compound-containing liquid crystal composition is negative.